The present invention is directed to compositions of matter suitable for use as photoprotectants or lightfastness enhancing agents. More specifically, the present invention is directed to oligomeric or polymeric siloxanes having thereon moieties imparting to the oligomers or polymers the ability to function as photoprotectants or lightfastness enhancing agents. One embodiment of the present invention is directed to a compound of one of the formulae
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 each, independently of the others, is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, R11 and R12 each, independently of the others, is an alkylene group, an arylene group, an arylalkylene group, or an alkylarylene group, G is a cationic moiety, A is an anionic moiety, n is an integer representing the number of repeat —OSi(R7)(R8)— monomer units, a is an integer representing the number of repeat —OSi(R10)(R12-lightfastness moiety)- monomer units, and c is an integer representing the number of repeat —OSi(R9)(R11-hydrophilic moiety)- monomer units.
Compositions for photoprotection of the skin and/or hair against ultraviolet radiation are known for use in sunscreens, cosmetics, hair products, and the like. Examples of such materials include aromatic compounds such as p-aminobenzoic acid derivatives, benzylidenecamphor derivatives, cinnamic acid derivatives, benzotriazole derivatives, and the like.
U.S. Pat. No. 6,270,214 (Smith et al.), the disclosure of which is totally incorporated herein by reference, discloses a process which comprises (a) applying to a substrate a fixing fluid which comprises a material selected from the group consisting of (1) block or graft copolymers of dialkylsiloxanes and polar, hydrophilic monomers capable of interacting with an ink colorant to cause the colorant to become complexed, laked, or mordanted, (2) organopolysiloxane copolymers having functional side groups capable of interacting with an ink colorant to cause the colorant to become complexed, laked, or mordanted, (3) perfluorinated polyalkoxy polymers, (4) perfluoroalkyl surfactants having thereon at least one group capable of interacting with an ink colorant to cause the colorant to become complexed, laked, or mordanted, and (5) mixtures thereof; (b) incorporating into an ink jet printing apparatus an ink composition which comprises water and a colorant which becomes complexed, laked, or mordanted upon contacting the fixing fluid; and (c) causing droplets of the ink composition to be ejected in an imagewise pattern onto the substrate.
U.S. Pat. No. 6,142,618 (Smith et al.), the disclosure of which is totally incorporated herein by reference, discloses a fluid deposition apparatus comprising (a) a fluid supply, (b) a porous fluid distribution member in operative connection with the fluid supply, enabling wetting of the fluid distribution member with a fluid, and (c) a porous metering membrane situated on the fluid distribution member, whereby the metering membrane enables uniform metering of the fluid from the fluid distribution member onto a substrate.
U.S. Pat. No. 6,124,376 (Nichols et al.), the disclosure of which is totally incorporated herein by reference, discloses a process which comprises incorporating into an ink jet printing apparatus an ink composition which comprises water, a colorant, and a polymer of the formula
wherein m, n, x, and y are each integers representing the number of repeat monomer units, and wherein the ratio of x:y is from about 10:90 to about 90:10, and causing droplets of the ink to be ejected in an imagewise pattern onto a recording sheet.
U.S. Pat. No. 6,200,369 (Schwarz), the disclosure of which is totally incorporated herein by reference, discloses an ink composition which comprises (a) water, (b) a colorant; and (c) an additive selected from the group consisting of diamido quaternary dialkyl ammonium salts, bitail quaternary tetraalkyl ammonium salts, bitail imidazolium salts, bitail biomimetic phospholipid salts, specific bisquaternary salts, β-hydroxyethyl ethylene diamine fatty acids, specific polyammonium salts, ethoxylated polyamine compounds, biquaternary pyridinium salts, aminofunctional polyorganosiloxanes, and mixtures thereof.
U.S. Pat. No. 6,106,599 (Breton et al.), the disclosure of which is totally incorporated herein by reference, discloses an ink composition comprising (1) an azole compound, (2) a viscosity compound, (3) a lightfastness component, (4) an antioxidant, and (5) a colorant.
U.S. Pat. No. 5,719,204 (Beach et al.), the disclosure of which is totally incorporated herein by reference, discloses polymeric dispersants used in formulating aqueous ink compositions, as well as inks containing those dispersants. The dispersants are graft copolymers comprising a hydrophilic polymeric segment, a hydrophobic polymeric segment incorporating a hydrolytically-stable siloxyl substituent, and a stabilizing segment, such as a reactive surfactant macromer, a protective colloid macromer, or a non-siloxyl hydrophobic monomer. The inks made with these dispersants show excellent stability, print characteristics, water-fastness, light-fastness, optical density, and in-use maintenance characteristics.
U.S. Pat. No. 5,686,633 (Vieira et al.), the disclosure of which is totally incorporated herein by reference, discloses a recording material for ink jet printing comprising a carrier having a surface which can be printed on or a carrier coated on one side with a material which can be printed on, wherein the carrier or the coating contains as a stabilizer at least one compound of the formula
in which R1 and R2 independently of one another are C1–C4 alkyl which is unsubstituted or substituted by one or two —OH, —COO-M+ and/or —SO3-M+ groups, C3–C5 alkenyl, C3–C5 alkynyl,
—CH2CH(OH)CH2—SO3-M+, —CO-alkyl(C1–C4) which is unsubstituted or substituted by —COORo or —CO—N(R5)(R6) or, if OR1 and OR2 are in the ortho position relative to one another, R1 and R2 together are C1–C6 alkylene, M+ being H+, a monovalent, divalent or trivalent metal cation or a group (R12′)N+(R12″)(R13′)(R14′), wherein R12′, R12″, R13 and R14 independently of one another are H, C1–C4 alkyl which is unsubstituted or substituted by 1 or 3 OH, C1–C4 alkyl interrupted by O, allyl, cyclopentyl, cyclohexyl, phenyl, benzyl or tolyl, or R1 is a group
in which p′ is a number from 2 to 6, R5 and R6 independently of one another are H or C1–C4 alkyl which is unsubstituted or substituted by an OH, COORo, —COO-M+, SO3-M+, P(O)(O-M+)2 or P(O)(ORo)2 group, R3′ and R4′ independently of one another are H, C1–C4 alkyl, OH or C1–C4 alkoxy, R3 and R4 independently of one another are H, halogen, —OR7, —COORo, —COO-M+, —OOC—R5, —CO—N(R5)(R6), —(R5)N—CO—R6, —CO—R5, —SO3-M+, —SO2N(R5)(R6), P(OR5)3, —(O)P—(O-M+)2, —(O)P—(ORo)2, C1–C8 alkyl which is unsubstituted or substituted by 1 to 7 —OR5 or —OO—C—R5 groups, by 1 or 2 —COORo, —COO-M+, or —CO—N(R5)(R6) groups or by one or two —SO3-M+, —SO2N(R5)(R6) or —(O)P—(ORo)2 or —(O)P(O-M+)2 groups, where M+, R5 and R6 are as defined above, or C5–C6 cycloalkyl or allyl, Ro being C1–C4 alkyl which is unsubstituted or substituted by an —OH group or —(CH2CH2O)r—H in which r is 1 to 12, and R7 being C1–C4 alkyl or —CO-alkyl(C1–C4) each of which is unsubstituted or substituted by 1 or 2 —OH groups or R3 and R4 independently of one another are one of the groups
in which R8 is a direct bond or methylene, R9 is H, C1–C8 alkyl, —COO-M+ or —SO3-M+, where M+, R1 and R2 are as defined above, R15 is —CO—, —(O)g—CpH2p—CO—, —OOC—CpH2p—, —COO—CpH2p—, —O—CH2CH(OH)—CH2— or
in which g is 0 or 1 and p is 1 to 6 and R24 is —OR5, —N(R5)(R6) or a group
and R16 is one of the following radicals:
in which R25 is H or C1–C4 alkyl, R17 is H, C1–C4 alkyl which is unsubstituted or substituted by an —OH group, —CH2—CH(OH)—CH2—OH, C1–C4 alkoxy, —OH, —CO-alkyl(C1–C4), —COCH═CH2, allyl, benzyl or a group
in which s is the number 2 or 3, t is a number from 0 to 2 and R21 and R22 independently of one another are H, C1–C4 alkyl or phenyl.
U.S. Pat. No. 5,643,356 (Nohr et al.), the disclosure of which is totally incorporated herein by reference, discloses an improved ink suitable for ink jet printing comprising a mixture of a colorant, an arylketoalkene stabilizing compound or a photoreactor, and a liquid vehicle, wherein the colorant is light-stable. When the photoreactor is combined with a wavelength-selective sensitizer to form a radiation transorber, the colorant is mutable upon exposure of the radiation transorber to specific, narrow bandwidth radiation. The colored composition may also contain a molecular includant having a chemical structure which defines at least one cavity wherein each of the colorant and photoreactor or radiation transorber is associated with the molecular includant. The invention also includes ink jet print cartridges containing the improved ink, ink jet printers containing the improved ink and methods of printing using the improved ink.
U.S. Pat. No. 5,610,257 (Richard et al.), the disclosure of which is totally incorporated herein by reference, discloses topically applicable sunscreen/cosmetic compositions well suited for enhanced photoprotection of human skin and/or hair against the damaging effects of UV-A and UV-B irradiation, particularly solar radiation, which comprise a photoprotecting effective amount of a novel benzotriazole-substituted polyorganosiloxane/polyorganosilane having one of the formulae (1) to (3):
A-Si(R′)3  (3)
wherein A is a monovalent benzotriazole radical which comprises an acrylate or acrylamide functional group, which is bonded directly to a silicon atom, and which has the formula (4):

U.S. Pat. No. 5,089,250 (Forestier et al.), the disclosure of which is totally incorporated herein by reference, discloses the cosmetic use, in particular for use as a UV filter, of benzotriazole diorganopolysiloxanes having either formula:
where R is C1–C10 alkyl, phenyl, or 3,3,3-trifluoropropyl, B is R or A, r=0–200, s=0–50, or formulas:
where u=1–20, t=0–20 and t+u>3. A and/or B represent a benzotriazole C3–C12 alkylene which may be substituted.
U.S. Pat. No. 4,256,493 (Yokoyama et al.), the disclosure of which is totally incorporated herein by reference, discloses a jet ink composition which comprises an aqueous jet ink containing a water-soluble dye, a wetting agent, and water as main components and, incorporated therein, a water-soluble ultraviolet absorbing agent as well as a metal salt, when necessary.
PCT Application WO 97/20000 (Nohr et al.), the disclosure of which is totally incorporated herein by reference, discloses colorant stabilizers and a colorant composition which includes a colorant and a colorant stabilizer. The colorant stabilizer imparts light stability to the colorant so that the colorant does not fade when exposed to electromagnetic radiation such as sunlight or artificial light.
European Patent Application EP 0867486 (Gangal et al.), the disclosure of which is totally incorporated herein by reference, discloses a jet printing ink composition which results in reduced drop misdirection and missing nozzles. The aqueous-based ink composition includes at least one colorant; a wetting agent; and a co-solvent comprising a substituted or unsubstituted lactam, an amide, or mixtures thereof.
Japanese Patent Publication JP 10278435, the disclosure of which is totally incorporated herein by reference, discloses a thermal recording medium having excellent recording traveling properties with excellent light resistance, heat resistance, and chemical resistance of a recorded part and white part. In the thermal recording medium comprising a thermal recording layer containing colorless or pale basic dye, colorant and a protective layer containing an ultraviolet absorbent sequentially provided on a support, the colorant is 1,1-bis(4-hydroxyphenyl)-1-phenylethane and the absorbent is N,N′-bis(2-hydroxy-3-(2H-benzotriazole-2-il)-5-methylbenzyl)-1,4-benzene-dicarboxyamide.
Japanese Patent Publication JP 11099740, the disclosure of which is totally incorporated herein by reference, discloses an ink jet recording sheet having superior light fastness of a recorded image, particularly superior light fastness of a magenta image, and also superior characteristics such as recording density and recording quality. At least one kind of compound like N-2-(3-(benzotriazole-2-yl)-4-hydroxyphenyl propionyl amino)ethyl-N,N,N-trimethyl ammonium chloride and others by a general formula
is contained in an ink jet recording sheet for forming a recorded image by using aqueous ink. In the formula, R1, R2, and R3 respectively represent hydrogen atom, C1–C4 alkyl or C1–C4 hydroxyalkyl and X represents organic or inorganic anion. (n) represents 0, 1, or 2 and (m) represents an integer of 2 to 6.
Japanese Patent Publication JP 2000141875, the disclosure of which is totally incorporated herein by reference, discloses a superior ink jet recording sheet of superior light fastness of a recorded image, particularly light fastness of a magenta image and free from the yellowing of surface, the deterioration of the picture quality and the like. A recorded image is formed on an ink jet recording sheet by using an aqueous ink, and in the recording sheet, at least one kind of benzotrizol compound represented by the formula
3-(3-(benzotriazol-2-yl)-4-hydroxyphenyl)decaglyceryl propionate or the like is contained in the recording sheet. In the formula, R1 represents a hydrogen atom or a 1–5C alkyl, and R2 represents a hydrogen atom or a chlorine atom. (m) represents 0 or 1–4 integer and (n) represents 1–12 integer.
Japanese Patent Publication JP 10007958, the disclosure of which is totally incorporated herein by reference, discloses an additive for a water based ink which is especially excellent in water resistance and can give a record with a high quality image hardly accompanied by blur of characters or images or border blur at the place where two colors are applied one on top of another. The additive is a polyorganosiloxane-modified amphiphilic polymer which has polyorganosiloxane units and is obtained by copolymerizing a hydrophilic ethylenically unsaturated monomer and a hydrophobic ethylenically unsaturated monomer, or polymerizing an amphiphilic ethylenically unsaturated monomer, in the presence of a polyorganosiloxane having mercaptized organic groups.
Japanese Patent Publication JP 10007969, the disclosure of which is totally incorporated herein by reference, discloses an ink composition excellent in light resistance, water resistance, and water repellency obtained by mixing a compound having a group having the function of stabilizing against ultraviolet rays with a specified amphipathic polymer. The composition is prepared by mixing a polar-solvent-soluble compound having the function of stabilizing against ultraviolet rays (e.g., hydroxyphenylbenzotriazole derivative) with an amphipathic polymer having polyorganosiloxane units, preferably obtained by radical-polymerizing a mixture comprising a hydrophilic ethylenically unsaturated monomer (e.g., acrylamide) and/or an amphipathic ethylenically unsaturated monomer (e.g., methoxypolyethylene glycol monomethacrylate) and optionally a hydrophobic ethylenically unsaturated monomer (e.g., methyl methacrylate) in the presence of an SH-containing polyorganosiloxane.
While known compositions and processes are suitable for their intended purposes, a need remains for improved lightfastness enhancing agents. In addition, a need remains for photoprotective compositions that can be employed in personal care products such as sunblocks, makeup, hair products, or the like.